Recovery of particulate carbon from synthesis gas

ABSTRACT

A process for recovering particulate carbon from the effluent gas stream from a partial oxidation synthesis gas generator by scrubbing the effluent gas with water in a scrubbing zone to form a carbon-water dispersion, mixing said dispersion in mixing and separating zones with a light liquid hydrocarbon fuel fraction extractant to produce a clarified water layer and a carbon-liquid hydrocarbon fuel dispersion, separating and recycling said clarified water to said scrubbing zone; separating said carbon light liquid hydrocarbon fuel dispersion and introducing same into a centrifugal separation zone; separately withdrawing from said centrifugal separation zone a thick stream of carbon-liquid hydrocarbon fuel dispersion and a separate thin stream of carbon-liquid hydrocarbon fuel dispersion; degasifying said clean centrifugal stream and introducing said thin centrifugal stream into said mixing and separating zone as a portion of said light liquid hydrocarbon fuel extractant, introducing said thick stream of carbon-liquid hydrocarbon fuel dispersion in admixture with fresh heavy liquid hydrocarbon fuel e.g. heavy fuel oil into a fractional distillation zone; recycling a light liquid hydrocarbon fuel fraction from said distillation zone to said mixing zone as a portion of said light liquid hydrocarbon fuel extractant, and introducing a pumpable bottoms slurry of carbon heavy liquid hydrocarbon fuel from said distillation zone into said synthesis gas generator as at least a portion of the fuel.

This is a division of application Ser. No. 535,607, filed Dec. 23, 1974,now U.S. Pat. No. 3,980,592.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a continuous process for recoveringparticulate carbon from synthesis gas, and particularly fromcarbon-water dispersions.

2. Description of the Prior Art

Raw synthesis gas leaving a partial oxidation synthesis gas generatorcomprises principally CO and H₂ together with minor amounts of finelydivided carbon or particulate carbon. Preferably, the particulate carbonmay be removed from the effluent gaseous stream by contacting the gaswith water in a quenching and scrubbing zone. The finely divided carbonsoot particles are wetted by water so as to form a mixture andparticulate carbon and water. The particulate carbon produced insynthesis gas manufacture is unique and problems associated with theseparation of synthesis gas carbon are not the same as those encounteredin the removal of carbon or solids made by other processes. For example,the fine carbon particles from partial oxidation are unusual in thatthey will settle in water to only about 1.0 to 3.0 weight percent,whereas conventional carbon blacks may settle to concentrations of asmuch as 10 weight percent.

To produce synthesis gas economically, it is important to separate clearwater from the carbon-water mixture for reuse. However, the fineparticle size of the carbon soot makes ordinary filtration methodsdiffuicult and makes gravity separation uneconomical because of excesssettling times i.e. about 1-2 days. Further, liquid hydrocarbonextraction procedures for recovering particulate carbon soot such asdisclosed in coassigned in U.S. Pat. No. 2,992,906 to F. E. Guptill, Jr.require large volumes of extractant. This in turn requires larger sizedauxilliary process equipment. Further, under some conditions troublesomeemulsions which are difficult to separate may form upon the addition ofa gas to the oil carbon dispersion. By the process of our invention,particulate carbon is quickly and easily separated from quench andscrubbing water, so as to permit recycle of the clear water and recycleof the extractant.

The oxo process is the commercial application of a chemical reactioncalled oxonation or, more properly, hydroformylation. In this reaction,hydrogen and carbon monoxide are added across an olefinic bond toproduce aldehydes containing one more carbon atom than the olefin.

The oxyl process is a method for directly producing alcohols bycatalytically reducing carbon monoxide with hydrogen so as to linkseveral partially reduced carbon atoms together. Essentially it is amodified Fischer-Tropsch Process which preferentially producesoxygenated compounds consisting mainly of alcohols.

SUMMARY

In one important aspect, the subject continuous process relates to amethod for producing clean synthesis gas including the steps of:

1. reacting by partial oxidation a hydrocarbonaceous fuel with a freeoxygen-containing gas in the reaction zone of a free-flow noncatalyticsynthesis gas generator at a temperature in the range of about 1300° to3500° F and a pressure in the range of about 1 to 300 atmospheres in thepresence of a temperature moderator to produce an effluent gas streamcomprising principally H₂ and CO and containing entrained particulatecarbon and at least one member of the group CO₂, H₂ O, H₂ S, COS, CH₄,A, and N₂ ;

2. introducing said effluent gas stream into gas-cooling andgas-scrubbing zones in which the gas stream is cooled and contacted withwater so as to effect the removal of said particulate carbon from saideffluent gas stream and producing a carbon-water dispersion;

3. removing gaseous impurities from the gas stream leaving (2) so as toproduce a stream of synthesis gas substantially comprising H₂ and CO;

4. contacting said carbon-water dispersion with a liquid extractantcomprising a light liquid hydrocarbon fraction produced in thedistillation zone in (6) and a thin centrifuge stream of carbon-lightliquid hydrocarbon fuel dispersion produced in (5), wherein the amountof said liquid extractant added to said carbon-water extractant issufficient to render all of the carbon particles in said carbon-waterdispersion hydrophobic and to resolve said carbon-water dispersion, andremoving a stream of clarified water and a separate stream ofcarbon-light liquid hydrocarbon fuel dispersion in a separating zone;

5. introducing said carbon-light liquid hydrocarbon fuel from (4) into acentrifugal separating zone, withdrawing from said centrifugalseparating zone a thick centrifuge stream of carbon-light liquidhydrocarbon fuel dispersion having a carbon content in the range ofabout 1 to 10 weight percent, and a comparatively thin centrifuge streamof carbon-light hydrocarbon fuel dispersion having a carbon content inthe range of about 0.02 to 1.0 weight percent; degasifying said thinstream and introducing said stream into said mixing zone in (4) aspreviously described as a portion of said liquid extractant, withdrawingsaid partially clarified water stream from said separating zone, andrecycling said water to said gas-scrubbing zone in (2) to scrub carbonfrom the effluent gas stream from the gas generator, introducing saidthick centrifuge stream of carbon-light liquid hydrocarbon fueldispersion in admixture with fresh heavy liquid hydrocarbon fuel into afractional distillation zone; and

6. removing a light liquid hydrocarbon fuel fraction from saiddistillation zone and recycling same to said mixing zone in (4) as aportion of said light liquid hydrocarbon fuel extractant; removing fromsaid distillation zone a pumpable bottoms slurry comprising particulatecarbon and the unvaporized portion of said heavy liquid hydrocarbon fueland introducing same into said synthesis gas generator as at least aportion of said fuel.

The synthesis gas may be produced at the proper pressure and H₂ /CO moleratio for direct feeding into an oxo or oxyl process. Advantageously, amixture of liquid organic by-products produced in said oxo or oxylprocess may be easily disposed of in the synthesis gas generator as aportion of the fuel.

DESCRIPTION OF THE INVENTION

Synthesis gas comprises principally H₂ and CO and may contain relativelysmall amounts of CO₂, H₂ O, CH₄, H₂ S, N₂, COS, A, particulate carbonand fuel ash. It may be made by the partial oxidation of ahydrocarbonaceous fuel in a free-flow synthesis gas generator. Forexample a liquid hydrocarbon fuel such as fuel oil is reacted with afree-oxygen containing gas and stream at an autogenously maintainedtemperature within the range of about 1300° to 3500° F. and a pressurein the range of 1 to 300 atmospheres.

By scrubbing the effluent gas stream from the gas generator with waterin a gas scrubbing zone, particulate carbon may be removed from the gasstream as a pumpable carbon-water dispersion containing about 0.5 to 3weight percent carbon. This carbon-water dispersion is then treated witha liquid hydrocarbon fuel extractant to separate the carbon from thewater. The extractant may comprise a light liquid hydrocarbon fuelfraction in admixture with a thin centrifuge stream of carbon-lightliquid hydrocarbon fuel dispersion. The light liquid hydrocarbon fuel isdescribed more fully later and may be selected from the group butanes,pentanes, hexanes, gasoline, kerosene, naphtha, light gas oils, andmixtures thereof.

The amount of light liquid hydrocarbonfuel extractant is sufficient torender all of the carbon particles in the carbon-water dispersionhydrophobic and to resolve the carbon-water dispersion. As furtherdescribed below, the extractant may be added in one or two stages. Thelight liquid hydrocarbon extractant forms with the carbon from thecarbon-water dispersion a pumpable carbon-light liquid hydrocarbon fueldispersion containing about 0.5 to 5 wt. % carbon. A clarified waterlayer separates out in a decanter and falls to the bottom. The waterlayer is removed from the decanter and may be recycled to the scrubbingzone. The carbon-extractant dispersion which forms and floats on thewater layer is removed and concentrated in a centrifugal separationzone.

The carbon-light liquid hydrocarbon fuel dispersion that is removed fromthe decanter is concentrated by means of centrifugal separation in acommercial centrifuge. Advantageously, by removing a portion of theliquid hydrocarbon fuel extractant in the overhead stream from thedecanter by centrifugal separation, the size and heat duty of theextractant stripper used downstream in the process may be reduced.Simultaneously, a thin centrifuge stream of light liquid hydrocarbonfuel containing a minor amount of carbon is produced. This thincentrifuge stream is then recycled to the mixer or to the decanter, orboth to resolve the carbon-water dispersion.

Industrial centrifuges such as described in Perry's Chemical Engineers'Handbook, by Perry, Chilton, and Kirkpatrick, Fourth Edition, McGrawHill, Pages 19-86 to 19-100, employ centrifugal acceleration which ismany times the gravitational acceleration. Centrifugal force causessedimentation of solid particles through a layer of liquid or filtrationof a liquid through a bed of porous solids. Centrifugal force, commonlyexpressed in multiples of the standard force of gravity, varies with therotational speed and with the radial distance from the center ofrotation.

Disc centrifuges for example illustrated in FIG. 19-139 of Perry'sChemical Engineers' Handbook develop 4,000 to 10,000 times the force ofgravity. Disc centrifuges have bowl diameters in the range of about 7 to32 inches, a disc spacing in the range of about 0.015 to 0.50 inches, anumber of discs in the range of about 30 to 130, and a disc half anglein the range of about 35 to 50. Disc centrifuges and other conventionalcentrifuges are suitable for use in the subject process.

The heavy (thick) centrifuges stream in admixture with heavy liquidhydrocarbon fuel is introduced into a conventional fractionaldistillation zone. The ratio of heavy liquid hydrocarbon fuel to lightliquid hydrocarbon fuel extractant in the thick centrifuge stream is inthe range of about 0.02 to 40 lb per lb. A light liquid hydrocarbon fuelfraction having an atmospheric boiling point in the range of about 100°to 500° F. is removed from said distillation zone, cooled, liquefied,and recycled to said mixing zone as the extractant.

The total amount of light hydrocarbon fuel fraction from thedistillation zone that is introduced into the decanter either in one ortwo-stage embodiments may be about 0.05 to 20 parts by weight of lightliquid hydrocarbon fuel per part by weight of thin centrifuge streamcomprising carbon-light liquid hydrocarbon fuel dispersion. In two-stagedecanter operation, preferably all of said thin centrifuge stream isintroduced into the decanter in the second stage. However, a smallportion i.e. up to 25 wt. % of the total amount of thin centrifugestream may in addition be introduced into the mixing zone in the firststage in addition with said light hydrocarbon fuel fraction. However,the thin centrifuge stream may be introduced into the first stage onlyin another embodiment.

A pumpable liquid bottoms slurry containing the particulate carbon fromsaid carbon-extractant dispersion from said distillation zone and theunvaporized portion of said heavy liquid hydrocarbon fuel is introducedinto said synthesis gas generator as at least a portion of said fuel.

Heavy liquid hydrocarbon fuels suitable for use in this process includefor example, heavy distillates, residual fuel oil, bunker fuel oil, No.6 fuel oil, and mixtures thereof. The carbon content of said bottomsslurry in wt. % is in the range of about 0.5 to 25. Advantageously, amixture of liquid organic by-products from an oxo or oxyl process in theamount of about 1 to 99 wt. % of the mixture so produced is mixed withsaid bottoms slurry. This mixture may be fed to the synthesis gasgenerator as feed. Alternatively, the mixture may be burned as fuel in afurnace. The clarified water from the separating zone is optionallypurified and recycled to said gas-scrubbing zone to scrub the effluentgas stream from the gas generator.

Gaseous impurities in the effluent gas stream from the synthesis gasgenerator may be removed in a manner to be more fully described toproduce synthesis gas e.g. mixtures of H₂ +CO having a mole ratio H₂ /COin the range of about 0.9 to 2.0 moles of H₂ per mole of CO. Synthesisgas may be produced having a specific H₂ /CO mole ratio for introductioninto said oxo or oxyl process.

In one embodiment of the invention, the mixtures of carbon monoxide andhydrogen produced in the synthesis gas generator are used as feed to thewell known oxo or oxyl catalytic process. Liquid organic by-productsfrom the oxo or oxyl process are then introduced into said synthesis gasgenerator as a portion of the fuel. Synthesis gas produced by thesubject process with a H₂ /CO mole ratio in the range of about 1-2 molesof the H₂ per mole of CO are introduced into the Oxo process wherecarbon monoxide and hydrogen are added to an olefin in the presence of acobalt catalyst at e.g. a temperature in the range of about 100° to 200°C and a pressure in the range of about 65 to 300 atmospheres to producean aldehyde containing one carbon atom more than the original olefin.Thus, a hydrogen atom and formyl group may be added across the doublebond of an olefin as shown in equations (1) and (2):

    RCH = CH.sub.2 + CO + H.sub.2 → RCH.sub.2 CH.sub.2 CHO (2)

    rch = ch.sub.2 + co + h.sub.2 → rch(cho)ch.sub.3    (2)

optionally, normal alcohols may be produced from the normal aldehydes byhydrogenation as shown in equation (3)

    RCH.sub.2 CH.sub.2 CHO + H.sub.2 → RCH.sub.2 CH.sub.2 CH.sub.2 OH (3)

the oxo reaction is homogeneously catalyzed by carbonyls of group VIIImetals, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium,irridium, and platinum. However, cobalt is the only metal whose carbonylcatalysts are of industrial importance e.g. CO₂ (CO)₈, HCo(CO)₄, and Co₄(CO)₁₂.

Reaction times vary in the range, of about 5 to 60 minutes. Thesynthesis gas feed to the oxo or oxyl process contains 1-2 moles ofhydrogen per mole of carbon monoxide.

Various olefinic raw materials include ethylene to producepropionaldehyde, propylene to produce butyraldehyde, and pentylenes,heptylenes, nonylenes, and dodecylenes used to produce higher oxoalcohols. Dimers and trimers of isobutylenes may be used. Straight chainproducts are favored over branched-chain products. For example, normalbut not isobutyraldehyde can be converted into butanol or2-ethyl-1-hexanol. Lower temperatures and higher carbon monoxidepressure favor the straight-chain isomer.

Processing steps required to produce an oxo product economically include(1) hydroformylation, or oxo reaction in an oxo reactor at a temperaturein the range of about 100°-200° C and a pressure in the range of about65-500 atm; (2) removal of catalyst from the reaction mixture(decobalting); (3) cobalt catalyst recovery and processing for reuse;(4) aldehyde product refining; and optionally, (5) hydrogeneration at atemperature in the range of about 50°-250° C, and a pressure in therange of about 50-3500 psi to produce alcohols; and (6) alcoholrefining. Oxo products, both aldehydes and alcohols are refined byconventional distillation equipment. Chemical treatment may be used toremove trace quantities of impurities.

The oxyl process is defined herein is a method for producing a mixtureof oxygenenated organic compounds by catalytically reducing carbonmonoxide with hydrogen at a temperature in the range of about 175° to450° C and a pressure in the range of about 10 to 200 atmospheres. TheH₂ /CO ratio may be in the range of about 0.9 to 2 moles of H₂ per moleof CO. Space velocities may range from 100 - 500 SCF of dry feed per cu.ft. of cat. per hr. and higher based on fresh feed. Both fused andprecipitated iron catalysts may be used. The iron catalyst may containcopper, calcium oxide, diatomite, and may be impregnated with potassiumhydroxide. Iron nitride catalysts may be used.

The oxyl process for producing alcohols may be illustrated by Equation(IV):

    2n H.sub.2 +  nCO → C.sub.n H.sub.2n .sub.+ 1 OH + (n-1) H.sub.2 O (IV)

the alcohols may be subsequently converted to olefins and paraffins.

Essentially the oxyl process is a modified Fisher-Tropsch process whichpreferentially produces oxygenated compounds consisting mainly ofalcohols. In addition to predominantly straight chain alcohols and fewside chains, by-product esters, other oxygen-containing compounds,paraffins, and olefin hydrocarbons may be produced. The olefins may betreated by the oxo process (hydroformylation followed by hydrogenation)to increase the yield of alcohols.

For example a mixture of aliphatic oxygenated compounds containingapproximately 30% alcohols in addition to acids, aldehydes, olefins, andesters may be produced by converting gaseous mixtures of H₂ + CO overalkalized iron fillings at 150 atmospheres pressure and at a temperatureof 400°-450° C.

Another oxyl process operates at a pressure in the range of about 10 to50 atmospheres and a temperature of about 175°-230° C. Fused ironcatalysts of the conventional ammonia-synthesis type and high spacevelocities are used. Gas recycle to increase the catalyst life may beemployed: 7-20 volumes of recycle gas per volume of fresh synthesis gas.Straight chain alcohols e.g. up to C₁₂, may be produced by this process.

By-products as defined herein are normally liquid organic co-productsformed in the hydroformylation or the oxyl process and consist of liquidorganic materials from the group consisting of alcohols, aldehydes,esters, ketones, ethers, acids, olefins, saturated hydrocarbons, andmixtures thereof.

A particular advantage of the subject invention is that the streamsynthesis gas may be produced in a synthesis gas generator at a properpressure for use in the oxo or oxyl process. A costly gas compressor maythereby be eliminated. Also, the mixture of liquid organic by-productsfrom the oxo or oxyl process, which may have previously presented adisposal problem may be now economically mixed with said carbon-heavyliquid hydrocarbon slurry bottoms from the distillation zone and burnedin the gas generator as fuel to produce more synthesis gas. The specificcomposition of the mixture of liquid organic by-products from the oxo oroxyl process will depend upon the reaction conditions, the type ofreactants, and the procedure used to refine the product. The amount ofeach constituent in the mixture may be taken from the ranges shown inTable I. This includes whole samples, fractions, and the raffinate afterwater extraction. If a group is present, there may be more than onecompound in that group present in the extractant. If for example themixture contains 65 wt. % of normal and isoalcohols and 5 wt. % ofesters, than the total remaining constituents in the mixture cannotexceed 30 wt. %. The term "by-products" includes by definition theliquid organic waste products from the oxo or oxyl process which havethe composition shown in Tables I and II.

                  TABLE I                                                         ______________________________________                                        INGREDIENTS IN LIQUID ORGANIC BY-PRODUCTS                                     Of Oxo or Oxyl Process                                                        ______________________________________                                        Group           Carbon Range Wt. %                                            ______________________________________                                        Alcohols        C.sub.3 to C.sub.16                                                                        2  to 75                                         Esters          C.sub.6 to C.sub.28                                                                        5  to 70                                         Aldehydes       C.sub.3 to C.sub.16                                                                        Nil to 25                                        Ketones         C.sub.3 to C.sub.16                                                                        Nil to 25                                        Ethers          C.sub.6 to C.sub.28                                                                        Nil to 50                                        Acids           C.sub.3 to C.sub.16                                                                        Nil to 10                                        Olefins         C.sub.5 to C.sub.15                                                                        Nil to 30                                        Saturated Hydrocarbons                                                                        C.sub.5 to C.sub.28                                                                        Nil to 50                                        Water                        Nil to 15                                        ______________________________________                                    

The ultimate analysis of the liquid organic by-products of the oxo oroxyl process is shown in Table II. The elements may be taken from theranges shown so long as the total wt. % is 100.

                  TABLE II                                                        ______________________________________                                        ULTIMATE ANALYSIS OF LIQUID ORGANIC BY-PRODUCTS                               of Oxo or Oxyl Process                                                        ______________________________________                                                        Wt. %                                                         ______________________________________                                        Carbon          About 55 to 90                                                Hydrogen        About  5 to 17                                                Oxygen          About  3 to 40                                                ______________________________________                                    

The preferred maximum concentration of organic acid present in themixture is less than 5 wt. %, for example 1-2 wt. %. The organic estersare the reaction products of primary saturated alcohols and lowmolecular weight saturated organic acids.

The composition of a typical liquid organic mixture, as produced forexample by the process shown in Hydrocarbon Processing, Page 211,November 1969, Gulf Publishing Co., Houston, Texas and comprising theliquid organic by-products of an oxo process is shown in Table III.

                  TABLE III                                                       ______________________________________                                        COMPOSITION OF TYPICAL MIXTURE                                                Comprising Liquid Organic By-Products From                                    Oxo Process                                                                   ______________________________________                                                          Wt. %                                                       Esters              56                                                        Ethers              20                                                        Aldehydes           5                                                         Ketones             5                                                         Acids               5      and below                                          Saturated hydrocarbons                                                                            1      and below                                          Olefins             1      and below                                          Alcohol             5                                                         Water               2                                                         ______________________________________                                    

The esters in the aforesaid mixture have an average C₁₂ number and areformed by the reaction of C₄ to C₉ alcohols and C₃ to C₈ acids. Theesters are highly branched and have an average C₁₂ number. The alcoholsinclude normal and isobutanol and isopropyl alcohol. The ultimateanalysis of said typical mixture is shown in Table IV.

                  TABLE IV                                                        ______________________________________                                        ULTIMATE ANALYSIS OF TYPICAL MIXTURE                                          Comprising Liquid Organic By-Products From                                    Oxo Process                                                                   ______________________________________                                                        Wt. %                                                                Carbon     69.2                                                               Hydrogen   12.0                                                               Oxygen     18.8                                                        ______________________________________                                    

Other properties of said typical mixture are shown in Table V.

                  TABLE V                                                         ______________________________________                                        Properties of Typical Mixture                                                 Comprising Liquid Organic By-Products                                         From Oxo Process                                                              ______________________________________                                        Gravity               API         29.2                                        Density,                           0.87                                       Viscosity,            Centistokes                                                          68° F         4.1                                                     122° F         2.0                                         Distillation,         ASTM                                                                Vol. %                ° F                                              IBP                   290                                                     10                    326                                                     20                    344                                                     30                    360                                                     40                    376                                                     50                    396                                                     60                    422                                                     70                    450                                                     80                    484                                                     90                    526                                                     95                    532                                                      EP                   564                                         ______________________________________                                    

The synthesis gas generator in my process preferably consists of acompact, unpacked, free-flow noncatalytic, refractory lined steelpressure vessel of the type described in coassigned U.S. Pat. No.2,809,104 issued to D. M. Strasser et al, which patent is incorporatedherewith by reference.

The free-oxygen containing gas may be selected from the group consistingof air, oxygen-enriched air (22 mole percent O₂ and higher), andpreferably substantially pure oxygen (95 mole percent O₂ and higher).

Preheating of the reactants is optional but generally desirable. Forexample, a hydrocarbon oil and steam may be preheated to a temperaturein the range of about 100° to 700° F. and the oxygen may be preheated toa temperature in the range of about 100° to 750° F.

A wide variety of hydrocarbonaceous fuels are suitable as feed stocksfor the partial oxidation process, either alone, in combination witheach other, or suitably in combination with said carbon-heavy liquidhydrocarbon fuel slurry from the distillation zone. Preferably, fromabout 0.01 to 99 parts by weight of fresh mixture of liquid organicby-products from an oxo or oxyl process may be mixed with each part byweight of the bottoms product from the fractional distillation zone, tobe further described.

The hydrocarbonaceous fuels include heavy and light liquid hydrocarbonfuels. Included are petroleum distillates and residue, gas oil, residualfuel, reduced crude, fuel oil, whole crude, coal tar oil, shale oil, tarsand oil, and mixtures thereof.

Pumpable slurries of solid carbonaceous feedstocks i.e., lignite,bituminous and anthracite coals in water or in said liquid hydrocarbonfuels are included herewith as within the scope of the definition forhydrocarbonaceous fuels which may be fed to the gas generator.Similarly, pumpable slurries of particulate carbon soot in a carrierfrom the group consisting of liquid hydrocarbon fuel or residuesthereof, liquid organic by-products from an oxo or oxyl process orresidues thereof, and mixtures thereof are also by definitionhydrocarbonaceous fuels which may be fed to the gas generator.

Light liquid hydrocarbon fuel extractant as used herein have thefollowing characteristics: atmospheric boiling point in the range ofabout 100° to 500° F., degrees API in the range of over 20 to about 100and a carbon number in the range of about 5 to 16.

Heavy liquid hydrocarbon fuels as used herein have a gravity in degreesAPI in the range of about -20 to 20.

It is normal to produce from hydrocarbonaceous fuels by partialoxidation about 0.5 to 20 weight percent of free carbon soot (basiscarbon in the hydrocarbonaceous fuel). The free carbon soot is producedin the reaction zone of the gas generator for example, by crackinghydrocarbonaceous fuels. Carbon soot will prevent damage to therefractory lining in the generator by constituents which are present asash components in residual oils. With heavy crude or fuel oils it ispreferable to leave about 2 to 3 weight percent of the carbon in thefeed as free carbon soot in the product gas. With lighter distillateoils, progressively lower carbon soot yields are taken.

The amount of soot in the product synthesis gas may be controlledprimarily by regulating the oxygen to carbon ratio (O/C atom/atom) inthe range of 0.7 to 1.5 atoms of oxygen per atom of carbon in the fueland to some extent by regulating the weight ratio of H₂ O to hydrocarbonfuel in the range of 0.15 to 3.0 pounds of H₂ O per pound of fuel. Inthe above relationship, the O/C ratio is to be based upon (1) the totalof free-oxygen atoms in the oxidant stream plus combined oxygen atoms inthe hydrocarbonaceous fuel feed molecules and (2) the total of carbonatoms in the hydrocarbonaceous fuel feed plus carbon atoms in recycledparticulate carbon (soot). Since the oxo and oxyl by-products containcombined oxygen atoms, the requirement of free-oxygen for gasificationis less than for ordinary hydrocarbons. In fact, there is a synergisticeffect leading to even lower oxygen consumption then would be expectedaccording to direct proportionality. H₂ O is principally introduced intothe reaction zone to help control the reaction temperature, to act as adispersant of the hydrocarbon fuel fed to the reaction zone, and toserve as a reactant to increase the relative amount of hydrogenproduced. Other temperature moderators include CO₂ -rich gas, a cooledportion of product gas, cooled off-gas from an integrated ore-reductionzone, nitrogen, and mixtures thereof.

Many advantages are achieved in the subject process by the addition ofoxygen containing hydrocarbon material, such as found in the liquidorganic by-product of the oxo or oxyl process, as a portion of the feedto the synthesis gas generator. For example, for a given level of sootproduction, the amount of free-oxygen supplied to the reaction zone ofthe synthesis gas generator, and the steam to fuel weight ratio may bedecreased at a substantial cost savings.

The free carbon soot leaving the reaction zone entrained in the streamof product synthesis gas has some unique properties. It is bothhydrophilic and oleophilic. It is easily dispersed in water and has ahigh surface area. For example, the specific surface area of the freecarbon soot, as determined by nitrogen absorption, ranges from 100 to1,200 square meters per gram. The Oil Absorption Number, which is ameasurement of the amount of linseed oil required to wet a given weightof carbon soot, ranges from 1.5 to 5 cc's of oil per gram of carbonsoot. For further information regarding the test method of determiningthe Oil Absorption Number see ASTM Method D-281.

Free carbon soot, also referred to herein as particulate carbon, asproduced within our process has a particle size in the range of about0.01 to 0.5 microns and commonly has a particle diameter of about 77millimicrons. Free carbon soot comprises about 92 to 94 weight percentof carbon, 0.1 to 4 weight percent of sulfur, and 3 to 5 weight percentof ash. Being formed at high temperatures, it is substantially free fromvolatile matter.

In one embodiment of our invention, the hot gaseous effluent from thereaction zone of the synthesis gas generator may be quickly cooled belowthe reaction temperature to a temperature in the range of 180° to 700° Fby direct quenching in water in a gas-liquid contacting or quenchingzone. For example, the cooling water may be contained in a carbon-steelquench vessel or chamber located immediately downstream from thereaction zone of said gas generator. A large diameter dip leg startingat the bottom end of the reaction zone and discharging beneath the waterlevel in the quench chamber serves as an interconnecting passage betweenthe reaction zone and the quench zone through which the hot productgases pass. This passage also serves substantially to equalize thepressure in the two zones. A concentric draft tube, open on both ends,may surround said dip leg, and create an annulus through which mixtureof quenched gas and water rises vigorously and splashes against thesupport plate of the reactor floor. The water and gas then separate inthe quench chamber in the space outside the draft tube. The circulationof water through the draft tube system maintains the entire quenchsystem at essentially the temperature of the water leaving the quenchvessel, which is also the temperature of the saturated steam in thequench zone.

Recycle water from the carbon scrubbing zone, to be further described isnormally introduced through a quench ring at the top of the dip-leg tocool the metal at that point. Large quantities of steam are generated inthe quench vessel, and the quench chamber may be likened to a highoutput high pressure boiler.

The turbulent condition in the quench chamber, caused by the largevolume of gases bubbling up through said annular space, helps the waterto scrub a large part of the solids from the effluent gas so as to forma dispersion of unconverted partuculate carbon and quench water.Further, steam required for any subsequent shift conversion step ispicked up by the effluent synthesis gas during quenching. For a detaileddescription of the quench chamber, reference is made to coassigned U.S.Pat. No. 2,896,927 issued to R. E. Nagle et al., which is herewithincorporated by reference. Any residual solids in the cooled andscrubbed effluent synthesis gas leaving the quench chamber may beremoved by means of a conventional venturi or jet scrubber, such asdescribed in Perry's Chemical Engineers' Handbook, Fourth Edition,McGraw-Hill Co., 1963, pages 18-55 to 56.

Alternately, the hot effluent gas stream from the reaction zone of thesynthesis gas generator may be cooled to a temperature in the range ofabout 240° to about 700° F. by indirect heat exchange in a waste heatboiler. The entrained solid particles may be then scrubbed from theeffluent synthesis gas by contacting and further cooling the effluentstream of synthesis gas with quench water in a gas-liquid contactapparatus, for example, a quench dip-leg assembly, a spray tower,venturi, or jet scrubber, bubble plate contactor, packed column, or in acombination of said equipment. For a detailed description of coolingsynthesis gas by means of a waste heat boiler and a scrubbing tower,reference is made to coassigned U.S. Pat. No. 2,999,741 issued to R. M.Dille et al and incorporated herewith by reference.

It is desirable to maintain the concentration of particulate carbon inthe gas cooling and scrubbing water streams in the range of about 0.5 -3 wt. % and preferably below about 1.5 wt. %. In this manner, thedispersion of carbon in water will be maintained sufficiently fluid foreasy pumping through pipelines and for further processing.

The temperature in the scrubbing zone is in the range of about 180° to700° F., and preferably in the range about 250°-550° F. The pressure inthe scrubbing zone is in the range of about 1-250 atmospheres, andpreferably at least 25 atmospheres. Suitably the pressure in thescrubbing zone is about the same as that in the gas generator, lessordinary pressure drop in the line.

It is important with respect to the economics of the process that theparticulate carbon be removed from the carbon-water dispersion and theresulting clear water to be recycled and reused for cooling andscrubbing additional particulate carbon from the synthesis gas. In thesingle stage embodiment of the subject process all of the previouslydescribed light liquid hydrocarbon fuel extractant in admixture with allof said thin centrifuge stream may be mixed with the carbon-waterdispersion at one time. The carbon water dispersion is thereby resolvedand the carbon is separated from the water. In this embodiment theamount by weight of said mixture of light liquid hydrocarbon fuel andthin centrifuge stream that is mixed with said carbon-water dispersionin a mixing zone is in the range of about 10 to 200 times, andpreferably in the range of about 20-100 times the weight of theparticulate carbon in the carbon-water dispersion. This amount issufficient to render all of said particulate carbon hydrophobic and toresolve the carbon-water dispersion. Clarified water separates from theparticulate carbon and a carbon-extractant dispersion is produced.

The carbon-water dispersion may be contacted with said light liquidhydrocarbon fuel extractant by any means e.g. mixing valve, staticmixer, baffled mixer, pump, orifice, nozzle, propeller mixer, or turbinemixer. High pressure will make possible the use of an extractant havinga lower boiling point. High temperature facilitates phase separation.

The mixed stream is passed into a phase separation zone, for example adecanter or tank providing a relatively quiescent settling zone. In theseparating zone, also known as a decanter, clarified water sinks to thebottom by gravity. A dispersion of carbon in said light liquidhydrocarbon fuel extractant may float on top of the clarified water. Thevolume of the settling tank should be sufficient to provide a suitableresidence time preferably of at least two minutes, and usually in therange of about 5 to 15 minutes.

The pressure in the settling zone or decanter should be sufficient tomaintain both the extractant and the water in liquid phase, e.g. 1 to200 atmospheres, depending upon temperature. The temperature, in thedecanter will be at or below that of the carbon-water dispersion leavingthe scrubbing zone e.g. ambient -700° F., and preferably in the range ofabout 200-550° F.

Clarified water is removed from the decanter, and at least a portion inadmixture with fresh water may be recycled to the scrubbing zone.Optionally, at least a portion of the dissolved water solubleconstituents from the extractant may be removed from the clarified waterby conventional means before the water is recycled to the scrubbingzone.

For example, the clarified water stream may be introduced into agas-liquid separation zone where the pressure is suddenly dropped. Alight gaseous fraction is flashed off which is cooled below the dewpoint to separate uncondensed light gases, water, and water solubleliquid hydrocarbon compounds. Clarified water is removed from theseparation zone and recycled to the scrubbing zone.

As previously mentioned, another embodiment of the invention involvestwo simultaneous additions of extractant in two stages. Thus in thefirst stage, the aforesaid carbon-water dispersion is resolved into aclarified water layer and a dry carbon powder which floats on theclarified water. This may be accomplished by adding the liquidhydrocarbon extractant to the carbon-water dispersion in an amount justsufficient to render all of the carbon hydrophobic but insufficient toproduce a carbon-extractant dispersion at this stage. As a result ofthis smaller amount of extractant, the carbon separates rapidly andsubstantially completely from the water and floats to the surface of theclarified water layer as a dry -- appearing unagglomerated soot.

The liquid hydrocarbon extractant introduced into the mixing zone in thefirst stage comprises a portion of said light liquid hydrocarbon fuelfraction obtained subsequently in the distillation zone. However, thelight liquid hydrocarbon fuel may be mixed with 0 to 25 weight % of thethin centrifuge stream. Further, optionally light liquid hydrocarbonfuel mak-up from an external source may be introduced into the mixingzone at this time.

The amount of liquid hydrocarbon extractant to be added may be obtainedexperimentally by shake tests. Small increments of extractant are addedto the carbon-water dispersion until the carbon separates rapidly andfloats on the surface of the clarified water. Thus when the water phaseis clear and the carbon is "dry" and fluffy, the amount of extractant isoptimum. The amount of extractant added in the first stage is about 1 to3 times the Oil Absorption No. of the particulate carbon in thecarbon-water dispersion. This may range between about 1.5 - 10 lbs. ofextractant per lb. of carbon or more likely in the range of about 1.5 tobelow 5.

In the second stage, the particulate carbon is floated off the surfaceof the clarified water layer by introducing a horizontal stream ofliquid extractant comprising at least a portion of said thin centrifugestream in admixture with a portion of said light liquid hydrocarbon fuelfraction from the distillation zone into said decanter at the interfacebetween said clarified water layer and said particulate carbon. Thesweeping action across the interface will also disperse the carbon inthe light liquid hydrocarbon fuel fraction.

The principal advantage of the two - stage addition of the liquidextractant lies in the avoidance of the formation of emulsions. In thefirst stage, the carbon-water dispersion is resolved and the carbonfloats to the surface of the water with the addition of a minimum ofliquid extractant. In the second stage the secondary extractant is addedin much larger amounts with a minimum of mixing with the water so thatemulsion formation is avoided even if emulsifying agents are present.

The amount of liquid extractant that is introduced into the second stageis sufficient to form a carbon-light liquid hydrocarbon fuel dispersioncontaining about 0.5-5 wt. % carbon. This amount may be about ten timesthe amount of extractant that was used in the first stage. The clarifiedwater is removed from the decanter in the manner described previously.

As previously mentioned, the carbon-extractant dispersion removedoverhead from the decanter may be concentrated by centrifugal separationand divided into a thick stream of carbon-light liquid hydrocarbon fueldispersion and a comparatively thin stream of carbon-light liquidhydrocarbon fuel dispersion. The thick stream may have a carbon contentin the range of about 1 to 10 wt. % and suitably about 4 to 7 wt. %. Thethin stream has a carbon content in the range of about 0.02 to 1.0 wt.%, and suitably about 0.1 to 0.5 wt. %. The thick stream ofcarbon-extractant is then passed into the distillation column inadmixture with fresh heavy liquid hydrocarbon fuel as previouslydescribed. This pumpable mixture may comprise about 0.02 to 40 andpreferably 0.1 1to 10 lbs of fresh heavy liquid hydrocarbon fuel per lbof light liquid hydrocarbon fuel in the thick centrifuge stream.

Prior to recycle to the mixing and separating zone, the comparativelyclean centrifuge stream of carbon-extractant may be passed into agas-liquid separator where any waste gas is removed.

The temperature and pressure in the decanter and centrifugal separationzone are preferably substantially the same.

The light hydrocarbon fuel fraction is removed from the conventionalfractional distillation column or stripping tower, cooled, liquefied,and recycled to said mixing zone, decanter, or both as said light liquidhydrocarbon fuel fraction extractant, as previously described.

The distillation or stripping tower is operated under suitableconditions for removing the carbon from said thick centrifuge stream byproducing said substantially carbon-free liquid hydrocarbon fuelfraction extractant, and also a pumpable residue slurry comprising saidparticulate carbon and the unvaporized portion of said heavy liquidhydrocarbon fuel. This residue slurry contains about 0.5 to 25 wt. %carbon and is removed from the bottom of the distillation column. It maybe passed in indirect heat exchange with incoming feed, and thenintroduced into said partial oxidation synthesis gas generator as atleast a portion of the feed. Fuel mixtures comprising about 1 to 99 wt.%, and preferably about 5 to 50 wt. % of said mixture of liquid organicby-products from the oxo or oxyl process and the remainder said bottomsslurry from the distillation column are preferably introduced into thesynthetic gas generator as feed. Alernately, said fuel mixture may beburned in a furnace, for example to produce steam. A suitable pressurein the distillation tower may be in the range of about 14.7 to 100 psig.Normally, conditions of temperature and pressure in said distillationcolumn are such that substantially no fractionation of the fresh heavyliquid hydrocarbon fuel takes place.

Although the process of the invention is particularly suitable forremoving substantially all of the dispersed particulate carbon from acarbon-water dispersion produced by water scrubbing the effluent gaseousstream from the partial oxidation process, it may be similarly used inmany other hydrocarbon gasification processes.

DESCRIPTION OF THE DRAWING AND EXAMPLES

A more complete understanding of the invention may be had by referenceto the accompanying schematic drawing which shows in FIG. 1 thepreviously described process in detail. Quantities have been assigned tothe various streams on an hourly basis so that the following descriptionin Example I may also serve as an example of the subject invention.

EXAMPLE I

In this embodiment of the continuous process, the decanter is operatedin a single stage. Referring to FIG. 1 of the drawing, on an hourlybasis about 14,400 lbs. of a particulate carbon-water dispersion at atemperature of about 250° F and containing about 144 lbs. of particulatecarbon from the gas scrubbing zone of a process for making synthesis gasby the partial oxidation of a hydrocarbonaceous fuel to be furtherdescribed are passed through line 1 into mixer valve 2 in which saidcarbon-water dispersion is mixed with about 10,727 lbs. of a lightliquid hydrocarbon fuel extractant from line 3. The liquid extractant inline 3 comprises 2,880 lbs. of light hydrocarbon fuel fraction fromlines 4 and 5, which is produced subsequently in the process infractional distillation column 6, to be further described, in admixturewith 7,847 lbs. of a thin centrifuge stream which is pumped by pump 7from holding tank 8 through lines 9 and 10. In the subject example thelight liquid hydrocarbon fuel is naphtha per ASTM D288. The thincentrifuge stream comprises a carbon dispersion of said light liquidhydrocarbon fuel extractant containing particulate carbon, to be furtherdescribed.

The mixture of light liquid hydrocarbon fuel extractant and carbon-wateris passed through line 14 into decanter 15. A relatively quiescentvolume is provided in the settling zone at a pressure of about 25atmospheres. Substantially clear water, containing substantially nodissolved water soluble constituents from said light liquid hydrocarbonfuel fraction extractant, settles by gravity to the bottom of decanter15 and is removed by way of line 16. If necessary, the water in line 16may be purified by conventional means and then recycled to the gascooling and scrubbing zone. A portion may be discharged from the systemand replaced with fresh water. 10,727 lbs. of said light liquidhydrocarbon fuel extractant in a dispersion of not less than 144 lbs. ofparticulate carbon together with any entrained water are removed nearthe top of decanter 15 by way of line 17 and are introduced into adisc-type centrifugal separator 18. The centrifuging speed correspondsto about 9500 revolutions per minute.

About 7,847 lbs. of a thin centrifuge stream of said light liquidhydrocarbon fuel extractant containing particulate carbon is removedfrom centrifuge 18 by way of line 19 and is introduced into holding tank8. Waste gas is discharged to a flare through line 20. Optionally, lightliquid hydrocarbon fuel make-up from an external source may be fed intothe system through line 21 valve 22 and line 23.

About 3024 lbs. of a thick centrifuge stream of particulatecarbon-extractant is removed from centrifuge 18 by way of line 24containing about 144 lbs. of particulate carbon. Thick centrifuge streamis mixed in line 25 with about 8,172 lbs. of a fresh heavy liquidhydrocarbon fuel feed from line 26. The heavy hydrocarbon fuel is aheavy fuel oil having the following characteristics: API 19.6, GrossHeating Value 17,814 BTU per lb., and Ultimate Analysis, Wt. % C 81.2,H, 11,4N 0.5, S 3.3, O 3.5 and Ash 0.2. The mixture in line 25 isintroduced into fractional distillation tower 6.

The operating conditions of distillation column 6 in this example aresuch that substantially none of the heavy liquid hydrocarbon fuel in themixture from line 25 is removed as a portion of the light hydrocarbonfraction leaving the column by way of line 27. In other wordssubstantially all of said heavy liquid hydrocarbon fuel feed passes outof the bottom of column through line 28 as a pumpable carbon slurrycontaining 144 lbs. of particulate carbon. The pressure in thedistillation column is about 15 psia.

The light liquid hydrocarbon fuel extractant in the thick centrifugestream charged to distillation column 6 is vaporized, and 3,606 lbs. arepassed overhead as a carbon-free stream through line 27. This stream isthen cooled and condensed in heat exchanger 29. The stream is passedthrough line 30 into liquid-liquid separator 31. Any water is drawn offthrough line 32. The light liquid hydrocarbon fuel extractant is pumpedby means of a pump 33 through line 34 and into line 35. About 2,880 lbs.of the light liquid hydrocarbon fuel extractant is passed through lines35, 4, 5, and 3 into mixing zone 2 as previously described as a portionof said single stage liquid extractant. The remainder of the liquidstream from line 35 i.e. 726 lbs. is recycled through line 36 intofractionation column 6. The recycle ratio for distillation column 6 mayrange from 0.05 to 0.5 lbs. of reflux in line 36 per lb. of extractantin the column feed in line 25.

A slip stream is removed from column 6 by way of line 40 and passedthrough reboiler 41 where the temperature is raised to the desiredtemperature for vaporizing the overhead fraction and recycled to column6 through line 42.

The bottoms carbon-oil slurry in line 28 comprising 8,172 lbs. of heavyliquid hydrocarbon fuel oil and 144 lbs. of particulate carbon arepumped by means of pump 43 into the reaction zone of a synthesis gasgenerator (not shown) as a portion of the fuel. Thus the bottoms slurrymay be pumped through line 44-46, vale 47, and line 48 into a synthesisgas generator (not shown).

Advantageously, a portion of the fresh mixture of liquid organicby-products from an oxo or oxyl process in line 53, to be furtherdescribed, is passed through vale 54, line 55 and into line 45 where itis mixed with said carbon-oil slurry from line 44. This improved liquidfuel mixture is then passed through lines 46 and 48 into said synthesisgas generator as at least a portion of the feed. Optionally, a portionof the mixture of fluids in line 45 may be introduced into a furnace(not shown) as fuel, by way of line 56, valve 57, and line 58.

Thus, in the subject process about 1,794 lbs. of liquid organicby-products from an oxo-process for the production of n-butyraldehydefrom line 53 are mixed in line 45 with 8,316 lbs. of carbon-heavy fueloil slurry from line 44. This mixture is then introduced into thesynthesis gas generator as said hydrocarbonaceous fuel and reacted with10,183 lbs. of oxygen (99.5 mole % O₂) and 4,395 lbs. of steam.

About 497,000 standard cubic feet (dry basis) of synthesis gas isproduced in a noncatalytic free-flow gas generator at a temperature ofabout 2400° F. and a pressure of about 37 atmospheres by the partialoxidation of said hydrocarbonaceous fuel feedstock. The composition ofthe synthesis gas in mole % follows: CO 41.00, H₂ 42.22, CO₂ 4.39,H_(2O) 11.26, CH₄ 0.21, A 0.11, N₂ 0.12, H₂ S 0.66, and COS 0.03. Afterpurification, as previously described, the mixture of H₂ and CO iscompressed and introduced into said oxo process for the production ofn-butyraldehyde.

EXAMPLE II

In this embodiment of the invention, the decanter is operated intwo-stages to improve performance. Aside from this, the rest of thecontinuous process is substantially the same as that describedpreviously in Example I.

With reference to FIG. 2 of the drawing, on an hourly basis in the firststage of the extraction operation with valve 60 open about 432 lbs. oflight liquid hydrocarbon fuel extractant from lines 35, 4, 61, 5, and 3are introduced into mixer 2 along with 14,400 lbs. of carbonwaterdispersion containing 144 lbs. of particulate carbon from line 1. Thisamount of liquid extractant is sufficient to render the particulatecarbon hydrophobic and to release substantially dry powdered carbon.

In the second stage of the decanter operation with valves 62 and 63open, simultaneously about 10,295 lbs. of extractant in acarbon-extractant dispersion are introduced to float off the carbonparticles and to form the carbon-light liquid hydrocarbon fueldispersion in line 17. The carbon-extractant in line 64 comprises lightliquid hydrocarbon fraction from distillation column 6 by way of lines35, 4, 65-67, and valve 63; and thin centrifuge steam from line 9, pump7, lines 10, 67, and valve 63.

Obviously, various modifications of the invention as herein before setforth may be made without departing from the spirit and scope thereofand therefore, only such limitations should be made as are indicated inthe appended claims.

I claim:
 1. A method for continuously producing clean synthesis gas forthe oxo or oxyl process comprising:1. reacting by partial oxidation ahydrocarbonaceous fuel or slurry of solid carbonaceous fuel with afree-oxygen containing gas in the reaction zone of a free-flownoncatalytic synthesis gas generator at a temperature in the range ofabout 1300° to 3500° F and at a pressure in the range of about 1 to 300atmospheres in the presence of a temperature moderator to produce aneffluent gas stream comprising H₂ and CO and containing entrainedparticulate carbon and at least one member of the group CO₂, H₂ O, H₂ S,COS, CH₄, A, and N₂ ;
 2. introducing said effluent gas stream into gascooling and gas scrubbing zones in which the gas stream is cooled andcontacted with water, effecting the removal of said particulate carbonfrom said effluent gas stream and producing a carbon-water dispersion;3. removing gaseous impurities from the gas stream leaving (2) producinga stream of synthesis gas substantially comprising H₂ and CO; 4.introducing the synthesis gas from (3) into an oxo or oxyl process andseparating therefrom a mixture of liquid organic by-products comprisingat least one alcohol and at least one ester, and at least oneconstituent from the group consisting of aldehydes, ketones, ethers,acids, olefins, saturated hydrocarbons and water;
 5. contacting saidcarbon-water dispersion with liquid organic extractant comprising lightliquid hydrocarbon fuel fraction having a gravity in degrees API in therange of over 20 to about 100 and a carbon number in the range of about5 to 16 and produced in the distillation zone in step (7) and a thincentrifuge stream of carbon-light hydrocarbon fuel dispersion producedin step (6) after removal of any waste gas wherein the amount of liquidorganic extractant introduced is sufficient to render all of the carbonparticles in said carbon-water dispersion hydrophobic and to resolvesaid carbon-water dispersion, and by decanting removing a stream ofclarified water and a separate stream of carbon-extractant dispersionhaving a carbon content of about 0.5 to 5 weight % in a separating zoneat a temperature in the range of ambient to 700° F and a sufficientpressure to maintain said liquid organic extractant and said clarifiedwater in liquid phase;
 6. introducing said carbon-extractant dispersionfrom (5) into a centrifuging zone at a temperature in the range of aboutambient to 700° F and a pressure in the range of about 1 to 200atmospheres, separately withdrawing from said centrifuging zone a thickstream of carbon-extractant having a carbon content in the range ofabout 1 to 10 weight percent, and a comparatively thin stream ofcarbon-extractant having a carbon content in the range of about 0.02 to1.0 weight percent; degasifying said thin stream and introducing saidstream into (5) as a portion of said liquid organic extractant,withdrawing said clarified water stream from said separating zone,optionally recycling said water to said gas-scrubbing zone in (2) toscrub carbon from the effluent gas stream from the gas generator,introducing said thick centrifuge stream of carbon-extractant inadmixture with fresh heavy liquid hydrocarbon fuel having a gravity indegrees API in the range of about b -20 to 20 and in the amount of about0.02 to 40 lbs. of fresh heavy liquid hydrocarbon fuel per lb. of lightliquid hydrocarbon fuel in said thick centrifuge stream into adistillation zone; and
 7. removing a light liquid hydrocarbon fuelfraction from said distillation zone and recycling same to (5) as aportion of said liquid organic extractant; removing from saiddistillation zone a pumpable bottoms slurry comprising particulatecarbon and the unvaporized portion of said heavy liquid hydrocarbonfuel, mixing with each part by weight of said pumpable bottoms slurryabout 0.01 to 99 parts by weight of said mixture of liquid organicby-products from the oxo or oxyl process in (4), and introducing sameinto said synthesis gas generator as at least a portion of saidhydrocarbonaceous fuel.
 2. The process of claim 1 wherein step (5) saidliquid organic extractant in an amount of about 10 to 200 times theweight of the particulate carbon in the carbon-water dispersion is mixedwith said carbon-water dispersion so that a carbon-extractant dispersionis produced which floats on the clarified water layer in the separatingzone.
 3. The process of claim 1 provided with the additional steps ofexpanding and dropping the pressure of the clarified water from step (6)and in a gas-liquid separation zone flashing off a light gaseousfraction; removing a clear substantially water stream from saidgas-liquid separation zone and introducing said clear substantiallywater stream to said gas-scrubbing zone to scrub the effluent gas streamfrom the gas generator; cooling said light gaseous fraction andseparating therefrom uncondensed light gases, water, and partially watersoluble liquid hydrocarbon compounds.
 4. The process of claim 1 providedwith the step of mixing supplemental light liquid hydrocarbon fuelmake-up with the liquid organic extractant in step (5).
 5. The processof claim 1 wherein said hydrocarbonaceous fuel is selected from thegroup consisting of various petroleum distillates and residue, gas oil,residual fuel, whole crude, fuel oil, reduced crude; coal tar oil; shaleoil; tar sand oil and mixtures thereof.
 6. The process of claim 1wherein said slurries of solid carbonaceous fuels are selected from thegroup lignite, bituminous coal, anthracite coal in water or liquidhydrocarbon fuels, and particulate carbon soot in liquid hydrocarbonfuels.
 7. The process of claim 1 wherein the contacting of saidcarbon-water dispersion in step (5) is effected in two stages includingin the first stage the step of mixing said carbon-water dispersion withabout 1.5-10 lbs. of the liquid organic extractant from the distillationzone in step (7) per lb. of carbon so as to render all of saidparticulate carbon hydrophobic and to release dry powdered carbon fromsaid carbon-water dispersion, with said carbon rising to the surface ofsaid water in said separating zone; and in the second stage introducinga stream of liquid organic extractant into said separating zone adjacentthe water surface to float off said carbon from the surface of thebottom layer of said clarified water while forming saidcarbon-extractant dispersion containing about 0.5 to 10 weight percentcarbon.
 8. The process of claim 7 wherein the amount of said liquidorganic extractant mixed with the carbonwater dispersion in the firststage on a weight basis is about 1 to 3 times the Oil Absorption Numberof the particulate carbon as determined by ASTM D 281-31.
 9. The processof claim 7 wherein said stream of liquid organic extractant in saidfirst stage comprises light liquid hydrocarbon fraction from saiddistillation zone in admixture with 0 to 25 weight percent of said thincentrifuge stream, and wherein the total amount of light hydrocarbonfuel fraction introduced into said second stage to float off said carbonis a mixture comprising about 0.05 to 20 parts by weight of light liquidhydrocarbon fuel fraction from said distillation zone from step (7) perpart by weight of said thin centrifuge stream from step (6).